CN103553078B - Technology for preparing ammonium sulfate by high-efficiency ammonia desulphurization and crystallization - Google Patents
Technology for preparing ammonium sulfate by high-efficiency ammonia desulphurization and crystallization Download PDFInfo
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- CN103553078B CN103553078B CN201310592368.7A CN201310592368A CN103553078B CN 103553078 B CN103553078 B CN 103553078B CN 201310592368 A CN201310592368 A CN 201310592368A CN 103553078 B CN103553078 B CN 103553078B
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- ammonium sulfate
- ammonium
- storage tank
- desulfurization
- flue gas
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- 229910052921 ammonium sulfate Inorganic materials 0.000 title claims abstract description 51
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 title claims abstract description 50
- 235000011130 ammonium sulphate Nutrition 0.000 title claims abstract description 50
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 title claims abstract description 28
- 238000002425 crystallisation Methods 0.000 title claims abstract description 18
- 230000008025 crystallization Effects 0.000 title claims abstract description 18
- 229910021529 ammonia Inorganic materials 0.000 title claims abstract description 14
- 238000005516 engineering process Methods 0.000 title abstract description 10
- 238000006477 desulfuration reaction Methods 0.000 claims abstract description 50
- 230000023556 desulfurization Effects 0.000 claims abstract description 44
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims abstract description 39
- 239000003546 flue gas Substances 0.000 claims abstract description 39
- PQUCIEFHOVEZAU-UHFFFAOYSA-N Diammonium sulfite Chemical compound [NH4+].[NH4+].[O-]S([O-])=O PQUCIEFHOVEZAU-UHFFFAOYSA-N 0.000 claims abstract description 34
- 238000000034 method Methods 0.000 claims abstract description 30
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 29
- 230000003009 desulfurizing effect Effects 0.000 claims abstract description 26
- 235000011114 ammonium hydroxide Nutrition 0.000 claims abstract description 23
- 230000008929 regeneration Effects 0.000 claims abstract description 18
- 238000011069 regeneration method Methods 0.000 claims abstract description 18
- 239000002002 slurry Substances 0.000 claims abstract description 18
- 238000006243 chemical reaction Methods 0.000 claims abstract description 14
- 238000001816 cooling Methods 0.000 claims abstract description 9
- 239000007788 liquid Substances 0.000 claims abstract description 9
- 238000000926 separation method Methods 0.000 claims abstract description 7
- 238000000889 atomisation Methods 0.000 claims description 30
- 230000003647 oxidation Effects 0.000 claims description 24
- AOSFMYBATFLTAQ-UHFFFAOYSA-N 1-amino-3-(benzimidazol-1-yl)propan-2-ol Chemical compound C1=CC=C2N(CC(O)CN)C=NC2=C1 AOSFMYBATFLTAQ-UHFFFAOYSA-N 0.000 claims description 12
- 239000000779 smoke Substances 0.000 claims description 10
- 238000001704 evaporation Methods 0.000 claims description 8
- 230000008020 evaporation Effects 0.000 claims description 8
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 6
- 229910052782 aluminium Inorganic materials 0.000 claims description 6
- 239000007787 solid Substances 0.000 claims description 6
- 239000004411 aluminium Substances 0.000 claims 2
- 238000005868 electrolysis reaction Methods 0.000 claims 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 15
- 239000001301 oxygen Substances 0.000 abstract description 15
- 229910052760 oxygen Inorganic materials 0.000 abstract description 15
- 238000004519 manufacturing process Methods 0.000 abstract description 6
- 238000005265 energy consumption Methods 0.000 abstract description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 abstract 2
- ZETCGWYACBNPIH-UHFFFAOYSA-N azane;sulfurous acid Chemical compound N.OS(O)=O ZETCGWYACBNPIH-UHFFFAOYSA-N 0.000 abstract 2
- 239000000428 dust Substances 0.000 abstract 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 2
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 2
- 238000005273 aeration Methods 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003337 fertilizer Substances 0.000 description 1
- 229910052602 gypsum Inorganic materials 0.000 description 1
- 239000010440 gypsum Substances 0.000 description 1
- 230000000222 hyperoxic effect Effects 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
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- Treating Waste Gases (AREA)
Abstract
The invention discloses a technology for preparing ammonium sulfate by high-efficiency ammonia desulphurization and crystallization, belonging to the field of a flue gas desulfurization and dust removal technology. The technology comprises the working procedures of desulphurization, oxidization and concentration and comprises the steps of firstly, filling flue gas and ammonia water into a desulphurization section of a desulfurizing tower, and feeding slurry which is generated after reaction and desulphurization and contains ammonium hydrogen sulfite and ammonium sulfite into a regeneration storage tank; filling the ammonia water into the regeneration storage tank to have reaction with the ammonium hydrogen sulfite to generate ammonium sulfite, then feeding the ammonium sulfite solution into an oxidization section of the desulfurizing tower, and feeding slurry which is generated by oxidization reaction between the ammonium sulfite and the flue gas and contains ammonium sulfate into a concentration storage tank; conveying the ammonium sulfate solution from the concentration storage tank into a cooling section of the desulfurizing tower, and enabling the ammonium sulfate solution to come into contact with the flue gas to exchange heat; concentrating the ammonium sulfate solution and then feeding the concentrated ammonium sulfate solution in a crystallization storage tank; conveying the product into a separator, and carrying out solid-liquid separation. The technology utilizes the characteristic that the flue gas is high in oxygen content, so that the ammonium sulfite oxidization efficiency is high, the crystallization velocity of the ammonium sulfate is improved, the equipment input and the production energy consumption are effectively reduced, the potential safety hazard of production is reduced, and the economic benefit is remarkable.
Description
Technical field
The invention belongs to flue gas desulfurization and dedusting technical field, be specifically related to a kind of technique of high-efficiency ammonia desulfurization crystalline ammonium sulfate.
Background technology
Flue gas desulfurization and dedusting can effective decreasing pollution, cleaner production environment, current flue gas desulfurization mainly contains dry method and wet method two class, the ammonia process of desulfurization in Wet Flue Gas Desulfurization Technique is one environmental protection more, efficiently technique compared with gypsum desulfurization, double alkali method desulfurizing, its primary product---ammonium sulfate is as important chemical fertilizer products, compare the product that other doctor treatment obtains and have higher economic worth, therefore ammonia-process desulfurization technique obtains in flue gas ash removal field and applies more and more widely.The technique of ammonia process of desulfurization crystalline ammonium sulfate adopted now mainly adopts ammoniacal liquor as desulfurizing agent, sulfur dioxide in itself and flue gas is reacted, and adopt and pass into compressed-air actuated method and make sulfite oxidation be ammonium sulfate, finally ammonium sulfate is concentrated, dry again.Owing to adopting pressurized aeration method oxidative ammonium, current technology technology adds operating cost undoubtedly, and the oxidation trough liquid level that the method requires is too high, is also unfavorable for the carrying out of keeping the safety in production.Therefore, research and development one can make full use of flue gas self oxygen content and be oxidized ammonium sulfite, effectively improves the new technology of ammonium sulfate crystallization efficiency, will have very good marketing prospect.
Summary of the invention
The object of the present invention is to provide a kind of technique of high-efficiency ammonia desulfurization crystalline ammonium sulfate.
The object of the present invention is achieved like this: a kind of technique of high-efficiency ammonia desulfurization crystalline ammonium sulfate, comprises desulfurization, oxidation, enrichment process, specifically comprise:
A, desulfurization: the ammoniacal liquor after flue gas to be desulfurization, atomization is passed into desulfurizing tower desulfurization section, the slurries containing ammonium bisulfite and ammonium sulfite generated after reaction desulfuration enter regeneration storage tank;
B, oxidation: ammoniacal liquor is passed into regeneration storage tank, after reacting and generate ammonium sulfite, then pass into desulfurizing tower oxidation panel by the ammonium sulfite solution after atomization with ammonium bisulfite, and the slurries containing ammonium sulfate generated after be oxidized with oxygen enrichment smoke reaction enter concentrated storage tank;
C, concentrated: to pass into desulfurizing tower cooling section by after the ammonium sulfate atomization in concentrated storage tank, with high-temperature flue gas contact heat-exchanging, after dilute ammonium sulfate solution evaporation and concentration, enter crystallization storage tank, then be delivered in separator and carry out Separation of Solid and Liquid.
Adopt technique of the present invention can make full use of the hyperoxic feature of electrolytic aluminum smoke self, oxidative ammonium efficiency is fast, and yield is high, by utilizing contact heat-exchanging, while to flue gas cool-down, improve the crystallization rate of ammonium sulfate, production efficiency is obviously improved.Owing to not needing to carry out pressurized aeration, technique of the present invention effectively reduces equipment investment and energy consumption, has saved production cost, remarkable in economical benefits.In addition, the ammonium sulfate crystallization technique after improvement, without the need to keeping higher oxidation trough liquid level, reduces potential safety hazard, further increases the application value of technology of the present invention.
Detailed description of the invention
The present invention is further illustrated below, but limited the present invention never in any form, and based on any conversion that training centre of the present invention is done, the present invention all falls into protection scope of the present invention.
A technique for high-efficiency ammonia desulfurization crystalline ammonium sulfate, comprises desulfurization, oxidation, enrichment process, specifically comprises:
A, desulfurization: the ammoniacal liquor after flue gas to be desulfurization, atomization is passed into desulfurizing tower desulfurization section, the slurries containing ammonium bisulfite and ammonium sulfite generated after reaction desulfuration enter regeneration storage tank;
B, oxidation: ammoniacal liquor is passed into regeneration storage tank, after reacting and generate ammonium sulfite, then pass into desulfurizing tower oxidation panel by the ammonium sulfite solution after atomization with ammonium bisulfite, and the slurries containing ammonium sulfate generated after be oxidized with oxygen enrichment smoke reaction enter concentrated storage tank;
C, concentrated: to pass into desulfurizing tower cooling section by after the ammonium sulfate atomization in concentrated storage tank, with high-temperature flue gas contact heat-exchanging, after dilute ammonium sulfate solution evaporation and concentration, enter crystallization storage tank, then be delivered in separator and carry out Separation of Solid and Liquid.
The each part of described desulfurizing tower is respectively cooling section, oxidation panel, desulfurization section from top to bottom.
The concentration of described ammoniacal liquor is 25 ~ 28%.
The oxygen content of described flue gas is 18 ~ 22%.
It is Oxygen Measuring Instrument that the oxygen content of described flue gas measures what adopt.
The volume ratio of described flue gas to be desulfurization and the ammoniacal liquor after being atomized is 350 ~ 450:1.
The preferred 400:1 of volume ratio of described flue gas to be desulfurization and the ammoniacal liquor after being atomized.
In described regeneration storage tank, the pH value of slurries is 5.5 ~ 6.5.
The volume ratio of the ammonium sulfite solution after described atomization and oxygen enrichment flue gas is 1:350 ~ 450.
The preferred 1:400 of volume ratio of the ammonium sulfite solution after described atomization and oxygen enrichment flue gas.
After described ammonium sulfite solution passes into desulfurizing tower, oxidation time is 120 ~ 180min.
Ammonium sulfate after described atomization and the volume ratio of high-temperature flue gas are 1:500 ~ 700.
Ammonium sulfate after described atomization and the preferred 1:600 of the volume ratio of high-temperature flue gas.
The time of staying of ammonium sulfate after described evaporation and concentration in crystallization storage tank is 30 ~ 60min.
Described flue gas is electrolytic aluminum smoke.
Described separator is cyclone hydraulic separators.
embodiment 1
A, desulfurization: by the ammoniacal liquor after flue gas to be desulfurization, atomization by volume 400:1 pass into desulfurizing tower desulfurization section respectively, the slurries containing ammonium bisulfite and ammonium sulfite generated after reaction desulfuration enter regeneration storage tank.
B, oxidation: ammoniacal liquor is passed into regeneration storage tank, the pH value controlling slurries in regeneration storage tank is 6.0, after ammoniacal liquor and ammonium bisulfite react and generate ammonium sulfite, again the ammonium sulfite solution after atomization is passed into desulfurizing tower oxidation panel, the volume ratio of the ammonium sulfite solution after atomization and oxygen enrichment flue gas is 1:400, oxidation 150min.The slurries containing ammonium sulfate that ammonium sulfite and oxygen enrichment smoke reaction generate enter concentrated storage tank.
C, concentrated: pass into desulfurizing tower cooling section by after the ammonium sulfate atomization in concentrated storage tank, with high-temperature flue gas contact heat-exchanging, the ammonium sulfate after atomization and the volume ratio of high-temperature flue gas are 1:600.Enter crystallization storage tank after dilute ammonium sulfate solution evaporation and concentration, be delivered in separator after stopping crystallization 45min and carry out Separation of Solid and Liquid.
embodiment 2
A, desulfurization: by the ammoniacal liquor after flue gas to be desulfurization, atomization by volume 380:1 pass into desulfurizing tower desulfurization section respectively, the slurries containing ammonium bisulfite and ammonium sulfite generated after reaction desulfuration enter regeneration storage tank.
B, oxidation: ammoniacal liquor is passed into regeneration storage tank, the pH value controlling slurries in regeneration storage tank is 6.5, after ammoniacal liquor and ammonium bisulfite react and generate ammonium sulfite, again the ammonium sulfite solution after atomization is passed into desulfurizing tower oxidation panel, the volume ratio of the ammonium sulfite solution after atomization and oxygen enrichment flue gas is 1:380, oxidation 120min.The slurries containing ammonium sulfate that ammonium sulfite and oxygen enrichment smoke reaction generate enter concentrated storage tank.
C, concentrated: pass into desulfurizing tower cooling section by after the ammonium sulfate atomization in concentrated storage tank, with high-temperature flue gas contact heat-exchanging, the ammonium sulfate after atomization and the volume ratio of high-temperature flue gas are 1:500.Enter crystallization storage tank after dilute ammonium sulfate solution evaporation and concentration, be delivered in separator after stopping crystallization 60min and carry out Separation of Solid and Liquid.
embodiment 3
A, desulfurization: by the ammoniacal liquor after flue gas to be desulfurization, atomization by volume 420:1 pass into desulfurizing tower desulfurization section respectively, the slurries containing ammonium bisulfite and ammonium sulfite generated after reaction desulfuration enter regeneration storage tank.
B, oxidation: ammoniacal liquor is passed into regeneration storage tank, the pH value controlling slurries in regeneration storage tank is 5.5, after ammoniacal liquor and ammonium bisulfite react and generate ammonium sulfite, again the ammonium sulfite solution after atomization is passed into desulfurizing tower oxidation panel, the volume ratio of the ammonium sulfite solution after atomization and oxygen enrichment flue gas is 1:420, oxidation 180min.The slurries containing ammonium sulfate that ammonium sulfite and oxygen enrichment smoke reaction generate enter concentrated storage tank.
C, concentrated: pass into desulfurizing tower cooling section by after the ammonium sulfate atomization in concentrated storage tank, with high-temperature flue gas contact heat-exchanging, the ammonium sulfate after atomization and the volume ratio of high-temperature flue gas are 1:650.Enter crystallization storage tank after dilute ammonium sulfate solution evaporation and concentration, be delivered in separator after stopping crystallization 30min and carry out Separation of Solid and Liquid.
Claims (5)
1. a technique for high-efficiency ammonia desulfurization crystalline ammonium sulfate, is characterized in that comprising desulfurization, oxidation, enrichment process, specifically comprises:
A, desulfurization: by the ammoniacal liquor after electrolytic aluminum smoke to be desulfurization, atomization by volume 350 ~ 450:1 pass into desulfurizing tower desulfurization section, the slurries containing ammonium bisulfite and ammonium sulfite generated after reaction desulfuration enter regeneration storage tank;
B, oxidation: ammoniacal liquor is passed into regeneration storage tank, control ph is 5.5 ~ 6.5, after ammoniacal liquor and ammonium bisulfite react and generate ammonium sulfite, again the ammonium sulfite solution after atomization is passed into desulfurizing tower oxidation panel, the ammonium sulfite solution after atomization and the electrolytic aluminum smoke slurries containing ammonium sulfate that 1:350 ~ 450 generate after coordinating oxidation reaction 120 ~ 180min by volume enter concentrated storage tank;
C, concentrated: to pass into desulfurizing tower cooling section by after the ammonium sulfate atomization in concentrated storage tank, with high-temperature electrolysis aluminium smoke contact heat exchange, after dilute ammonium sulfate solution evaporation and concentration, enter crystallization storage tank, then be delivered in separator and carry out Separation of Solid and Liquid.
2. the technique of high-efficiency ammonia desulfurization crystalline ammonium sulfate as claimed in claim 1, is characterized in that each part of described desulfurizing tower is respectively cooling section, oxidation panel, desulfurization section from top to bottom.
3. the technique of high-efficiency ammonia desulfurization crystalline ammonium sulfate as claimed in claim 1, is characterized in that the concentration of described ammoniacal liquor is 25 ~ 28%.
4. the technique of high-efficiency ammonia desulfurization crystalline ammonium sulfate as claimed in claim 1, is characterized in that the volume ratio of the ammonium sulfate after described atomization and high-temperature electrolysis aluminium flue gas is 1:500 ~ 700.
5. the technique of high-efficiency ammonia desulfurization crystalline ammonium sulfate as claimed in claim 1, is characterized in that the time of staying of the ammonium sulfate after described evaporation and concentration in crystallization storage tank is 30 ~ 60min.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103908797B (en) * | 2014-04-10 | 2015-12-30 | 攀钢集团西昌钢钒有限公司 | The feed system of crystallizer and feed process |
| CN104740987B (en) * | 2015-03-20 | 2017-06-27 | 凯天环保科技股份有限公司 | A kind of resource ammonia desulfurizing process |
| CN107983106A (en) * | 2017-11-29 | 2018-05-04 | 北京铝能清新环境技术有限公司 | A kind of flue gas purification system of low-temperature ammonium method production aluminium oxide |
| CN110368816A (en) * | 2018-04-13 | 2019-10-25 | 江苏新世纪江南环保股份有限公司 | Oxidation method and device for ammonia desulphurization solution |
| CN110787618A (en) * | 2019-11-12 | 2020-02-14 | 新疆生产建设兵团第八师天山铝业股份有限公司 | Power plant and aluminum electrolysis flue gas series-connection desulfurization method |
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|---|---|---|---|---|
| WO1988007024A1 (en) * | 1987-03-13 | 1988-09-22 | Fuel Tech, Inc. | Process for the reduction of nitrogen oxides in an effluent using sugar |
| CN1887408A (en) * | 2005-06-28 | 2007-01-03 | 镇江市江南环保设备研究所 | Void tower type ammonia desulfurizing process and apparatus |
| CN101143291A (en) * | 2006-09-13 | 2008-03-19 | 史选增 | Low-consumption high-quality ammonium sulfate fertilizer recovery wet ammonia process desulfurizing technology |
| CN102228777A (en) * | 2011-05-23 | 2011-11-02 | 潍坊恒安散热器集团有限公司 | Double-oxidation ammonia desulfurization process and device |
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- 2013-11-22 CN CN201310592368.7A patent/CN103553078B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1988007024A1 (en) * | 1987-03-13 | 1988-09-22 | Fuel Tech, Inc. | Process for the reduction of nitrogen oxides in an effluent using sugar |
| CN1887408A (en) * | 2005-06-28 | 2007-01-03 | 镇江市江南环保设备研究所 | Void tower type ammonia desulfurizing process and apparatus |
| CN101143291A (en) * | 2006-09-13 | 2008-03-19 | 史选增 | Low-consumption high-quality ammonium sulfate fertilizer recovery wet ammonia process desulfurizing technology |
| CN102228777A (en) * | 2011-05-23 | 2011-11-02 | 潍坊恒安散热器集团有限公司 | Double-oxidation ammonia desulfurization process and device |
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